铈锆对甲烷部分氧化制合成气钯催化剂催化性能的影响
摘要
随着石油资源日益枯竭,天然气资源不断开发,以天然气为优质、清洁能源和化工原料越来越受到人们的关注。甲烷部分氧化制合成气因能耗低,可显著降低设备投资和生产成本;反应速率快;生成的合成气H2/CO为2,可直接用于甲醇及费-托合成等优点而成为国内外研究的热点。
本文以等体积浸渍法制备Pd负载的α-Al_2O_3和CeO_2-ZrO_2系列催化剂,测试样品负载量和煅烧温度对催化性能的影响,对比CeO_2-ZrO_2和α-Al_2O_3载体在甲烷部分氧化反应中的催化性能;进一步以共沉淀法制备三种不同混合方式的CeO_2-ZrO_2/Al_2O_3混合载体,采用等体积浸渍法制备Pd/CeO_2-ZrO_2/Al_2O_3催化剂,考察CeO_2-ZrO_2/Al_2O_3混合载体在甲烷部分氧化反应中的催化性能,揭示载体不同的混合方式对甲烷部分氧化催化剂催化性能的影响。利用XRD、BET、TPR、Raman和TG-DTA对样品的晶相、比表面、表面性质和积炭进行了研究。
研究表明,以CeO_2-ZrO_2为载体能减少活性组分Pd的负载量,能提高甲烷部分氧化催化剂的活性和稳定性。这要归因于CeO_2-ZrO_2载体能提高活性组分分散度和CeO_2-ZrO_2中的晶格氧参与反应。Pd/CeO_2-ZrO_2/Al_2O_3不同混合方式样品中,分子混合样品具有最佳的稳定性,这是因为分子混合样品的金属-载体具有较强的相互作用,活性组分的抗烧结能力较强;金属与CeO_2-ZrO_2接触的界面较大,CeO_2-ZrO_2中的晶格氧能及时消除金属上的积炭。催化剂的失活是由活性组分烧结和催化剂积炭共同作用造成的。催化剂上积炭以石墨的形式存在,并且主要位于载体的酸性位上。
With the gradually depletion of fossil energy, a great deal of interest has grown in using natural gas as high quality, clean energy and chemical raw. Methane partial oxidation is weak exothermic and the process needs less energy and capital cost than the conventional endothermic steam reforming. Moreover, the reaction rate is very fast and the H2: CO ratio of about 2 is suitable for downstream processes such as Fischer-Tropsch synthesis. So the methane partial oxidation is paid much attention in recently years.
In this paper, mixing supports CeO_2-ZrO_2/Al_2O_3 with three different mixing methods were prepared by co-precipitation method and theα-Al_2O_3, CeO_2-ZrO_2 and CeO_2-ZrO_2/Al_2O_3 supported Pd catalysts were prepared by impregnation method. The catalytic performance of methane partial oxidation was investigated on Pd/α-Al_2O_3, Pd/CeO_2-ZrO_2 and Pd/CeO_2-ZrO_2/Al_2O_3 catalysts. The influence of Pd loading, calcaning temperature and supports effect on the catalytic performance was compared on Pd/α-Al_2O_3 and Pd/CeO_2-ZrO_2 catalysts. The effect of mixing support and mixing methods on the catalytic performance was also studied. Catalysts were characterized by XRD, BET, TPR, Raman spectra and TG-DTA techniques.
The results indicate that CeO_2-ZrO_2 supporter may reduce the Pd loading content and CeO_2-ZrO_2 supported catalyst takes on higher catalytic performance and stability, which might be attributed to the better dispersion of Pd and oxygen storage capacity of CeO_2-ZrO_2. Among the three Pd/CeO_2-ZrO_2/Al_2O_3 sampls, molecular mixing sample behaves the higher stability, this might be explained by stonger intereaction between Pd and support, and larger interface between metal and CeO_2-ZrO_2. Metal sintering and carbon deposition are the main reason for the deactivation of catalysts after 24h reaction. Carbon deposited on the catalysts is in the form of graphite and mostly deposited on the acid sites of the supports.
本文以等体积浸渍法制备Pd负载的α-Al_2O_3和CeO_2-ZrO_2系列催化剂,测试样品负载量和煅烧温度对催化性能的影响,对比CeO_2-ZrO_2和α-Al_2O_3载体在甲烷部分氧化反应中的催化性能;进一步以共沉淀法制备三种不同混合方式的CeO_2-ZrO_2/Al_2O_3混合载体,采用等体积浸渍法制备Pd/CeO_2-ZrO_2/Al_2O_3催化剂,考察CeO_2-ZrO_2/Al_2O_3混合载体在甲烷部分氧化反应中的催化性能,揭示载体不同的混合方式对甲烷部分氧化催化剂催化性能的影响。利用XRD、BET、TPR、Raman和TG-DTA对样品的晶相、比表面、表面性质和积炭进行了研究。
研究表明,以CeO_2-ZrO_2为载体能减少活性组分Pd的负载量,能提高甲烷部分氧化催化剂的活性和稳定性。这要归因于CeO_2-ZrO_2载体能提高活性组分分散度和CeO_2-ZrO_2中的晶格氧参与反应。Pd/CeO_2-ZrO_2/Al_2O_3不同混合方式样品中,分子混合样品具有最佳的稳定性,这是因为分子混合样品的金属-载体具有较强的相互作用,活性组分的抗烧结能力较强;金属与CeO_2-ZrO_2接触的界面较大,CeO_2-ZrO_2中的晶格氧能及时消除金属上的积炭。催化剂的失活是由活性组分烧结和催化剂积炭共同作用造成的。催化剂上积炭以石墨的形式存在,并且主要位于载体的酸性位上。
With the gradually depletion of fossil energy, a great deal of interest has grown in using natural gas as high quality, clean energy and chemical raw. Methane partial oxidation is weak exothermic and the process needs less energy and capital cost than the conventional endothermic steam reforming. Moreover, the reaction rate is very fast and the H2: CO ratio of about 2 is suitable for downstream processes such as Fischer-Tropsch synthesis. So the methane partial oxidation is paid much attention in recently years.
In this paper, mixing supports CeO_2-ZrO_2/Al_2O_3 with three different mixing methods were prepared by co-precipitation method and theα-Al_2O_3, CeO_2-ZrO_2 and CeO_2-ZrO_2/Al_2O_3 supported Pd catalysts were prepared by impregnation method. The catalytic performance of methane partial oxidation was investigated on Pd/α-Al_2O_3, Pd/CeO_2-ZrO_2 and Pd/CeO_2-ZrO_2/Al_2O_3 catalysts. The influence of Pd loading, calcaning temperature and supports effect on the catalytic performance was compared on Pd/α-Al_2O_3 and Pd/CeO_2-ZrO_2 catalysts. The effect of mixing support and mixing methods on the catalytic performance was also studied. Catalysts were characterized by XRD, BET, TPR, Raman spectra and TG-DTA techniques.
The results indicate that CeO_2-ZrO_2 supporter may reduce the Pd loading content and CeO_2-ZrO_2 supported catalyst takes on higher catalytic performance and stability, which might be attributed to the better dispersion of Pd and oxygen storage capacity of CeO_2-ZrO_2. Among the three Pd/CeO_2-ZrO_2/Al_2O_3 sampls, molecular mixing sample behaves the higher stability, this might be explained by stonger intereaction between Pd and support, and larger interface between metal and CeO_2-ZrO_2. Metal sintering and carbon deposition are the main reason for the deactivation of catalysts after 24h reaction. Carbon deposited on the catalysts is in the form of graphite and mostly deposited on the acid sites of the supports.
引文
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